Polymerization catalyst and method

ABSTRACT

A catalyst and method in which the catalyst is used with an aluminum cocatalyst in the polymerization and copolymerization of 1-olefins and is prepared by reacting a monofunctional organic silicon compound with silica, alumina, or the like followed by reacting the product of this reaction with a Group IIA organometallic compound or complex, then reacting this product with a halide or alkoxide of a metal of Group IVB or Group VB or mixtures thereof. If desired, the halide or alkoxide may be first reacted with the silicon compound reaction product before the reacting with the organometallic compound or complex.

BACKGROUND OF THE INVENTION

The catalysts of this invention are produced by (1) reacting amonofunctional organic silicon compound with silica or alumina or amixture thereof, (2) reacting the product of (1) with a Group IIAorganometallic compound or complex of magnesium or calcium, and (3)reacting the product of (2) with a halide or alkoxide of titanium,vanadium, zirconium or mixtures of these, or (2') reacting the productof (1) with an alkyl aluminum halide and a Group IIA organometalliccompound or complex of magnesium or calcium prior to (3), or (1')reacting the product of (1) with the halide or alkoxide of (3) prior to(2).

K. Ziegler first discovered two component catalysts based on compoundsof the Group IVB-VIB metals of the periodic table and an organometalliccompound belonging to Groups I-IIIA of the periodic table for thepolymerization of olefins. Since his discovery, numerous catalysts havebeen disclosed as improvements over the original Ziegler catalysts. Mostof these catalyst systems are of relatively low activity and stability.They require a costly catalyst removal step.

One of the modifications attempted in an effort to increase the activityof the Ziegler type catalyst was to deposit the catalyst components onan inert support. In U.S. Pat. No. 2,981,725 such a process isdisclosed. The supports used were magnesium chloride, silicon carbide,silica gel, calcium chloride, etc. The activity of the catalystsdisclosed in this patent was still low.

Recently several catalyst systems have been disclosed in which titaniumor vanadium halides are reacted with magnesium containing supports suchas magnesium alkoxide, magnesium hydroxy chloride, etc. U.S. Pat. Nos.3,654,249; 3,759,884; 4,039,472; 4,082,692 and 4,097,409 describe suchcatalysts. In catalysts that contain silica, a thermal activation ofsilica prior to deposition of the catalyst components is necessary.

None of these patents disclose the methods and products of thisinvention.

SUMMARY OF THE INVENTION

This invention provides novel catalysts, methods of making them andmethods for the polymerization and copolymerization of alpha-olefins.These catalysts are especially useful for the polymerization of ethyleneto high density polyethylene, and for the copolymerization of ethylenewith alpha-olefins for the formation of medium and low densitycopolymers. These improved catalysts are highly active and are wellsuited for the economical and energy efficient particle form and gasphase processes. Specifically, the object of this invention is toimprove the well known Ziegler type catalyst by the method of thisinvention. These improved catalysts can be easily adapted to theparticle form or gas phase process plants. Polymers made using theinvention catalysts can have high MI and narrow molecular weightdistribution. Thus, polymers well suited for injection molding androtational molding applications can be manufactured. The catalysts ofthis invention are stable, particulate, and easy flowing.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The catalysts of this invention have higher reactivity in olefinpolymerization than normal Ziegler catalysts. The reaction of organicsilicon compounds with silica or alumina is the critical step inobtaining higher reactivity. This is shown by comparative examples.Since the silica does not need to be thermally activated at hightemperatures, the cost of the fuel used for heating and the cost of thefurnace or other equipment can be avoided. Furthermore, the losses ofmaterial which are frequently encountered in operations such as heatingin a fluidized bed can also be avoided. The catalysts described by thisinvention are suitable for economic gas phase or particle formprocesses. The polymers made by this catalyst do not need a postreaction step to remove the catalyst residues. In a particle formprocess, the polymers are particulate in nature and do not show foulingtendencies compared to prior art catalysts.

This invention consists of improved catalysts for the polymerization ofalpha-olefins. The catalysts are made by first reacting a monofunctionalorganic silicon compound with silica or alumina. The reaction product issubsequently reacted with a Group IIA organometallic compound orcomplex. After completing this reaction, a halide or alkoxide of GroupIVB or VB metal is added. The resulting solid component is separated bysolvent evaporation or solvent filtration. The solid catalyst componentis fed to the polymerization reactor along with an alkyl aluminumcompound. The silica can have minor amounts of titania, zirconia,magnesia, etc.

The Group IIA metals that are especially useful in this inventioninclude calcium and magnesium.

The Group IVB and Group VB metals that are especially useful in thisinvention include titanium, zirconium and vanadium.

The preferred titanium compound may be selected from the followingformulas:

    TiX.sub.4

    (R'O).sub.m Ti(OR').sub.n

    TiX.sub.m (OR').sub.(4-m)

in which m is 1, 2, 3 or 4, n is 0, 1, 2 or 3 and m plus n equals 4; R'is selected from alkyl, aryl, cycloalkyl, alkaryl, cyclopentadienyl andalkenyl, for example, ethenyl, propenyl and isopropenyl, each of thesegroups having 1 to 12 carbon atoms, and X is halogen. When more than oneR' group occurs in the titanium compound, the groups can be the same ordifferent. The halides and haloalkoxides of titanium are preferred.

The quantity of titanium metal used in the process of the presentinvention is suitably in the range of 0.05-50.0% based on the weight ofthe support material, and preferably in the range of 0.5-20.0%.

The Group IVB and VB metal halide or alkoxide is preferred. Mixtures ofGroup IVB and VB compounds can also be used. The concentration of theGroup IVB and VB metal in the catalyst can vary from 0.1-20.0 wt. %based on the weight of the catalyst.

The Group IIA organometal compounds are preferably the alkyls or arylsof magnesium or its complexes such as that with alkyl aluminumcompounds. The structural formulae of some preferred compounds are R₂ Mgand (R₂ Mg)_(n).AlR₃ where R is alkyl containing 1-10 carbon atoms oraryl such as phenyl, naphthyl and cyclopentadienyl and n is 0.5-10.Complexes of organomagnesium compounds with organoaluminum halides canalso be used.

The ratio by weight of Group IIA metal to the Group IVB and VB metal canvary from 0.1-100 even though 0.1-20 is the preferred range. The metalalkyls or aryls may also contain a halide in addition to the organicmoiety.

The silica can be dried at 100°-200° C. to remove the surface water orit can be used as it is before the reaction with the organosiliconcompounds. The organosilicon compounds are those that react with thesurface hydroxyl groups on silica or alumina. Examples of thesecompounds have the following structures: (R₃ Si)₂ NH, R₃ Si(OR), R₃ SiXand (R₃ Si)₂ O where R is alkyl or aryl, preferably each containing 1 to20 carbon atoms, and X is halogen. Specific examples are hexamethyldisilazane, trialkylsilyl ethoxide, alkyl chlorosilanes, etc. Thereaction of silica with the organosilicon compound can be done in anyconvenient way, i.e., in solution, direct liquid-solid reaction, vaporphase reaction, etc. In the reaction of the organosilicon compounds withsilica or alumina an excess of the organosilicon compounds is used tofacilitate a complete reaction. After the reaction of silica or aluminawith the organosilicon compound, it should not be thermally treated butshould be stripped of any excess organosilicon compound and by-productsof the reaction by vacuum suction, solvent washing in which thepreferred solvent is a liquid hydrocarbon or by purging with a gas. Thiscan be done at a temperature between ambient and about 200° C.

The alkyl aluminum cocatalyst can be chosen from trialkyl aluminumcompounds and alkyl aluminum hydride compounds and their mixtures. Thealkyl groups of suitable cocatalysts have hydrocarbon chains containingone or about ten carbon atoms and may be straight-chained or branched.Triaryl aluminum compounds may also be used but because they are not soreadily obtained as the alkyl compounds they are not preferred. Examplesof suitable cocatalysts are triethylaluminum, trioctyl aluminum,tri(2-methyl pentyl)aluminum and diethyl aluminum hydride. Triisobutylaluminum and diisobutylaluminum hydride are especially preferred. Ifneeded, alkyl aluminum halides may be used along with the alkyl aluminumcompounds described above.

The cocatalyst may be fed to the polymerization reactor along with theabove-described solid component in the same or preferably separatelines. The molar ratio of the cocatalyst to the Group IVB and VB metalcompounds in the solid component can be from 0.1:1 to 100:1 although thepreferred range is 1:1 to 20:1.

When using the catalyst according to the invention at least one 1-olefinof the formula R--CH═CH₂, where R is hydrogen or a straight chain orbranched alkyl radical having from 1 to 10, preferably from 1 to 8,carbon atoms is polymerized. Examples of such olefins are ethylene,propylene, butene-1, hexene-1, 4-methyl-pentene-1, octene-1. Ethylene ispolymerized alone or as a mixture consisting of at least 70% by weightof ethylene and at most 30% by weight of a 1-olefin of the aboveformula.

The polymerization may be carried out in suspension, solution or in thegaseous phase, continuously or discontinuously, at a temperature of from20°-150° C., preferably from 60°-110° C., under a pressure of from 100psi to 1000 psi gauge. It is carried out preferably under thetechnically interesting pressure in the range of from 300-800 psi.

The melt index of the polyethylene produced by the invention catalystcan be controlled by methods known to the art such as increasing thetemperature of polymerization or by the addition of hydrogen. Thesecatalysts show relatively high activity in ethylene polymerization andcopolymerization. The polymers can be easily blended with antioxidantsand pelletized for commercial use. High partial pressures of hydrogencan be used to yield very high melt index products.

To summarize, therefore, the catalyst of this invention is prepared by(1) reacting a monofunctional organosilicon compound with silica oralumina or mixtures, (2) reacting the product of (1) with a Group IIAorganometallic compound or complex, and (3) reacting the product of (2)with a halide or alkoxide of a metal of Group IVB or Group VB ormixtures of said halide or alkoxide. The solid catalyst product of (3)is used with an alkyl or aryl aluminum compound prior to and/or duringthe polymerization reaction.

The catalysts are useful for producing polymers of 1-olefins of 2 to 8carbon atoms and copolymers of these with 1-olefins of 2 to 20 carbonatoms to form solid polymers or copolymers.

The reactant of step (1) above with the organosilicon compound ispreferably silica or alumina or mixtures of these but may also be withthoria, zirconia, titania, magnesia or mixtures of these or mixtureswith silica or alumina or both.

EXAMPLE 1 (Comparative)

A catalyst was prepared from Davison Chemical Company Grade 952 silica.The reactions were conducted in a dry, nitrogen purged flask immersed inan ice water bath. First 3.3 grams of the silica was added and thesilica was stirred for thirty minutes at the low temperature. Then 20.8ml of a (Bu₂ Mg)₆.5 Et₃ Al solution in heptane (10% wt.) was added bysyringe (1.46 grams of complex). The mixture was stirred for thirtyminutes and then 1.13 ml (1.92 grams) of titanium tetrachloride wasadded. After an additional thirty minutes at 0° C. the flask was placedin a bath at 90° C. and the solvent was evaporated under nitrogen flow.A portion of the catalyst was tested in a pressure vessel usingisobutane diluent at a total pressure of 550 psig at 221° F. with ahydrogen partial pressure of 50 psig. TIBAL was added to give 9.2 mmoles per gram of solid catalyst. The reactivity was found to be 2445g/g cat/hr. (34,500 g/g Ti/hr).

EXAMPLE 2 (Silane Treated Silica)

A catalyst was prepared in the same way as in Example 1 except that thesilica had been treated with hexamethyl disilazane. The reactions werealso conducted at room temperature instead of 0° C. The polymerizationtest with this catalyst shows that it is much more reactive than thecatalyst made with the untreated Davison Grade 952 silica. Under thesame conditions, the reactivity was found to be 8570 g/g cat/hr.(122,000 g/g Ti/hr).

EXAMPLE 3

In a three-necked flask which has been purged free of air with nitrogenwas placed 10 grams of hexamethyldisilazane-treated Davison 952 silica.10 cc of ethylaluminum sesquichloride (25% solution in heptane), 10 ccof (Bu₂ Mg)₆.5 Et₃ Al (10% solution in heptane) and 1.5 cc of titaniumtetraisopropoxide solution (20% in pentane) were syringed into theflask. A portion of the dry brown powder was used in ethylenepolymerization at 223° F. using TIBAL as a cocatalyst. The reactivity ofthe catalyst was 4402 g/g cat/hr.

EXAMPLE 4 (Comparative)

In this experiment the silane treated silica was replaced with untreatedDavison 952 silica, dried at 560° C. Otherwise, conditions were the sameas the example above. The reactivity of this catalyst was only 1477 g/gcat/hr.

EXAMPLE 5

Into a nitrogen-purged 250 ml three-necked flask was placed 1.9 grams ofhexamethyldisilazane-treated silica. The nitrogen purging was continuedfor an additional one hour to remove any entrapped air in the silanetreated silica. 18.5 cc of (_(n) --Bu₂ Mg)₇.5 Et₃ Al in a 5 wt. %solution in heptane was added to the flask and the contents were stirredfor 1/2 hour. 0.47 ml of titanium tetrachloride, calculated to give 6.1wt. % titanium on the final catalyst, was added with stirring. The wholereaction mixture turned black in color. After 1/2 hour, this catalystwas dried at 90° C. with a nitrogen purge. About 16.3 mg of this drypowder was placed in a nitrogen purged 1300 ml stainless steel reactorheld at 215° F. Triisobutyl aluminum (TIBAL) was added to the reactor togive an Al/Ti ratio of about 7. The reactor was closed and 500 ml ofisobutane was metered in. 50 pounds of hydrogen was pressured into thereactor. Ethylene was continuously fed to the reactor to maintain atotal constant pressure of 550 psig. After one hour of polymerizationthe polymer was recovered by flash evaporation of the solvent. Thereactivity of the catalyst was found to be 9202 g/g cat/hr. The meltindex of the polyethylene was 0.28 (ASTM D-1238 52T). An R_(d) of 2.7was measured for this polymer indicating narrow molecular weightdistribution. The R_(d) value was measured as described in the articlein Polymer Engineering and Science, Vol. II, pages 124-128 (1971).

EXAMPLE 6 (Comparative)

A catalyst similar to the above example was prepared. Ethylenepolymerization in the absence of triisobutyl aluminum showed reactivityof only 419 g/g cat/hr.

The following examples show that silane treated silica is not aneffective ingredient with certain catalyst compositions. The dataindicates that an organometal compound of Group IIA is necessary for thedesired effect.

EXAMPLE 7 (Comparative)

2.2 grams of silica which was dried at 120° C. was placed in a nitrogenpurged flask. It was treated with 11.02 ml of diethylaluminum chloridesolution (25.5% by weight in heptane). This mixture was stirred for 0.5hour. Subsequently 0.54 ml of TiCl₄ was added to the reaction flask andstirring was continued for another 0.5 hour. The catalyst was dried at90° C. Ethylene was polymerized using this catalyst with TIBAL as acocatalyst. The reactivity was 859 g/g cat/hr.

EXAMPLE 8

In this example silica was replaced with hexamethyl disilazane treatedsilica. Other conditions were similar to the above control example. Thereactivity in ethylene polymerization was 816 g/g cat/hr. This indicatesthat silane treated silica is not effective with certain catalystingredients. Similar comparisons with TIBAL in place of diethylaluminumchloride did not give improvement in activity with silane treated silicacompared to untreated silica.

The following examples show the catalyst in this invention givespolyethylene with narrower molecular weight distribution.

EXAMPLE 9

A 2 liter three-necked flask was purged with nitrogen.Hexamethyldisilazane-treated silica (200 grams) dried in an oven at 110°C. was placed in the flask. It was again purged free of air. 345 ml of a10% heptane solution of (n-C₄ H₉)₂ Mg₆.5 (C₂ H₅)₃ Al was added slowlywith stirring. 500 ml of dry heptane was added to make a slurry. Thereaction was allowed to continue for 5 hours. TiCl₄ (28 ml) was addeddropwise over a 2 hour period. Stirring of the reaction mixture wascontinued for 16 hours. The catalyst was dried at 90° C. with a purge ofnitrogen. The final catalyst contained 4.2% titanium. This catalyst wasused in ethylene polymerization in a continuous particle form reactor at218° F. 1.5 mol percent hydrogen was used to regulate the MI. Thepolymer produced has an R_(d) of 5.4 and MI of 5.0.

EXAMPLE 10 (Comparative)

A similar catalyst as above was made with unmodified silica thermallyactivated at 600° C. Ethylene was polymerized at 218° F. with thiscatalyst along with 1.5 mol percent hydrogen. The polymer had 6 MI buthad an R_(d) of 8.9 indicating broader molecular weight distribution.

EXAMPLE 11

In a nitrogen purged dry 500 ml three-necked flask was placed 2.4 gramsof hexamethyl disilazane treated silica. The hexamethyl disilazanesilica was used without any thermal treatment. 23.4 ml of (n-C₄ H₅)₂Mg₇.5 (C₂ H₅)₃ Al (5% solution in heptane) was syringed into the flaskwith stirring. The reaction was allowed to proceed for one hour. TiCl₄(0.60 ml) was added dropwise to give 6.1% titanium on the catalyst. Thereaction was continued for 1/2 hour. The contents were dried at 94° C.for 0.75 hour. The dry powder was dark brown in color. 50.7 ml of thiscatalyst was used along with triisobutyl aluminum in ethylenepolymerization (Al/Ti=7.2). 50 psi hydrogen partial pressure and 550psig total pressure was used. The reaction temperature was 215° F. Thereactivity of this catalyst was 7976 g/g cat/hr.

EXAMPLE 12

In this experiment the catalyst from the above example was used withtri-n-hexyl aluminum as a cocatalyst (Al/Ti=7.2). The reactivity inethylene polymerization was 6991 g/g cat/hr.

EXAMPLE 13

In this example the catalyst from Example 11 was used along withtriisobutyl aluminum as a catalyst. This was used in ethylene-hexene-1copolymerization to give polyethylene with 0.953 density.

Having described our invention as related to the embodiments set outherein, it is our intention that the invention be not limited by any ofthe details of description, unless otherwise specified, but rather beconstrued broadly within its spirit and scope as set out in the appendedclaims.

We claim:
 1. A solid catalyst for use with an alkyl or aryl aluminumcompound cocatalyst in the polymerization and copolymerization of1-olefins, and prepared by: (1) reacting a halogen free monofunctionalorganic silicon compound with silica or alumina having surface hydroxylgroups or a mixture thereof, said silicon compound being reactive withsaid surface hydroxyl groups; (2) reacting the product of (1) with aGroup IIA organometallic compound, or complex of an alkyl aluminumcompound, of magnesium or calcium; and (3) reacting the product of (2)with a halide or alkoxide of titanium, vanadium, zirconium or mixturesof these; or (2') reacting the product of (1) with an alkyl aluminumhalide and a Group IIA organometallic compound, or complex of an alkylaluminum compound, of magnesium or calcium prior to (3); or (1')reacting the product of (1) with the halide or alkoxide of (3) prior to(2).
 2. The catalyst of claim 1 wherein the metal of step (3) is in aconcentration of about 0.1-20 weight percent of said solid product. 3.The catalyst of claim 1 wherein said Group IIA compound or complex of(2) comprises an alkyl or aryl of magnesium or a magnesium complex. 4.The catalyst of claim 1 wherein the weight ratio of the Group IIA metalcompound to the Group IVB or VB metal compound is from 0.1-100.
 5. Thecatalyst of claim 4 wherein said weight ratio is about 0.1-20.
 6. Thecatalyst of claim 1 wherein one or more of said organometallic compoundscontains a halide in addition to the organic moiety.
 7. The catalyst ofclaim 1 wherein said reaction of (1) is with silica which has beenpredried at about 100°-200° C. for a time sufficient to remove surfacewater prior to said reaction.
 8. The catalyst of claim 1 wherein saidorganic silicon compound in (1) is in stoichiometric excess therebyfacilitating a complete reaction, and said excess is later removed. 9.The catalyst of claim 1 wherein the product of (1) is separated from anyunreacted organic silicon compound and reaction by-products.
 10. Thecatalyst of claim 9 wherein said separation is by vacuum suction. 11.The catalyst of claim 9 wherein said separation is by purging with a gasinert to the product of (1).
 12. The catalyst of claim 9 wherein saidseparation is at a temperature between ambient and 200° C.
 13. Thecatalyst of claim 1 wherein said cocatalyst is a trialkyl aluminum, analkyl aluminum hydride or a mixture thereof.
 14. The catalyst of claim13 wherein said cocatalyst is an alkyl aluminum and the alkyl groupscomprise hydrocarbon chains that are straight or branched and each chaincontains about 1 to 10 carbon atoms.
 15. The catalyst of claim 1 whereinsaid cocatalyst comprises an aryl aluminum compound.
 16. The catalyst ofclaim 1 wherein said aluminum compound comprises an alkyl aluminum, analkyl aluminum halide or a mixture thereof.
 17. The catalyst of claim 1wherein said aluminum compound comprises a trialkyl aluminum or an alkylaluminum hydride.
 18. The catalyst of claim 1 wherein the cocatalystaluminum compound is in a molar ratio with the product of (3) of from0.1-100 to
 1. 19. The catalyst of claim 18 wherein said ratio is fromabout 1-20 to
 1. 20. The method of making a solid catalyst for use withan alkyl or aryl aluminum compound cocatalyst in the polymerization andcopolymerization of 1-olefins by: (1) reacting a halogen freemonofunctional organic silicon compound with silica or alumina havingsurface hydroxyl groups or a mixture thereof, said silicon compoundbeing reactive with said surface hydroxyl groups; (2) reacting theproduct of (1) with a Group IIA organometallic compound, or complex ofan alkyl aluminum compound, of magnesium or calcium; and (3) reactingthe product of (2) with a halide or alkoxide of titanium, vanadium,zirconium or mixtures of these; or (2') reacting the product of (1) withan alkyl aluminum halide and a Group IIA organometallic compound, orcomplex of an alkyl aluminum compound, of magnesium or calcium prior to(3); or (1') reacting the product of (1) with the halide or alkoxide of(3) prior to (2).
 21. The method of claim 20 wherein the metal of step(3) is in a concentration of about 0.1-20 weight percent of said solidproduct.
 22. The method of claim 20 wherein said Group IIA compound orcomplex of (2) comprises an alkyl or aryl of magnesium or a magnesiumcomplex.
 23. The method of claim 20 wherein the weight ratio of theGroup IIA metal compound to the Group IVB or VB metal compound is from0.1-100.
 24. The method of claim 23 wherein said weight ratio is about0.1-20.
 25. The method of claim 20 wherein one or more of saidorganometallic compounds contains a halide in addition to the organicmoiety.
 26. The method of claim 20 wherein said reaction of (1) is withsilica which has been predried at about 100°-200° C. for a timesufficient to remove surface water prior to said reaction.
 27. Themethod of claim 20 wherein said organic silicon compound in (1) is instoichiometric excess thereby facilitating a complete reaction, and saidexcess is later removed.
 28. The method of claim 20 wherein the productof (1) is separated from any unreacted organic silicon compound andreaction by-products.
 29. The method of claim 28 wherein said separationis by vacuum suction.
 30. The method of claim 28 wherein said separationis by purging with a gas inert to the product of (1).
 31. The method ofclaim 28 wherein said separation is at a temperature between ambient and200° C.
 32. The method of claim 20 wherein said cocatalyst is a trialkylaluminum, an alkyl aluminum hydride or a mixture thereof.
 33. The methodof claim 32 wherein said cocatalyst is an alkyl aluminum and the alkylgroups comprise hydrocarbon chains that are straight or branched andeach chain contains about 1 to 10 carbon atoms.
 34. The method of claim20 wherein said cocatalyst comprises an aryl aluminum compound.
 35. Themethod of claim 20 wherein said aluminum compound comprises an alkylaluminum, an alkyl aluminum halide or a mixture thereof.
 36. The methodof claim 20 wherein said aluminum compound comprises a trialkyl aluminumor an alkyl aluminum hydride.
 37. The method of claim 20 wherein thecocatalyst aluminum compound is in a molar ratio with the product of (3)of from 0.1-100 to
 1. 38. The method of claim 37 wherein said ratio isfrom about 1-20 to
 1. 39. The catalyst of claim 1 wherein the Group IIAmetal of (2) comprises magnesium and the reaction of (3) is performedwith titanium.
 40. The method of claim 20 wherein the Group IIA metal of(2) comprises magnesium and the reaction of (3) is performed withtitanium.
 41. A catalyst for use with an alkyl or aryl aluminum compoundcocatalyst in the polymerization and copolymerization of 1-olefins, andprepared by: (1) reacting a halogen free monofunctional organic siliconcompound with silica or alumina or a mixture thereof; (2) reacting theproduct of (1) with a Group IIA organometallic compound or complex ofmagnesium or calcium; and (3) reacting the product of (2) with a halideor alkoxide of titanium, vanadium, zirconium or mixtures thereof toproduce a solid catalyst product.
 42. The method of making a catalystfor use with an alkyl or aryl aluminum compound cocatalyst in thepolymerization and copolymerization of 1-olefins by: (1) reacting ahalogen free organic monofunctional silicon compound with silica ofalumina or a mixture thereof; (2) reacting the product of (1) with aGroup IIA organometallic compound or complex of magnesium or calcium;and (3) reacting the product of (2) with a halide or alkoxide oftitanium, vanadium, zirconium or mixtures thereof to produce a solidcatalyst product.
 43. A solid polymerization catalyst component preparedby mixing:(a) a support obtained by reacting silica having surfacehydroxyl groups with a halogen free monofunctional silylating compoundwhich is reactive with said surface hydroxyl groups, with (b) anorganomagnesium compound including a component of the formula MgR₂ whereR is a hydrocarbon radical, and (c) a tetravalent titanium compound. 44.A method of making a solid polymerization catalyst component by thesteps of mixing(a) a support obtained by reacting silica having surfacehydroxyl groups with a halogen free monofunctional silylating compoundwhich is reactive with said surface hydroxyl groups, with (b) anorganomagnesium compound including a component of the formula MgR₂wherein R is a hydrocarbon radical, and (c) a tetravalent titaniumcompound.